DE102008042523A1 - Triblock copolymer comprising e.g. hydrocarbon radical, block-B and anchor block-C containing respective statistical copolymers, and block-D containing homo or copolymer of N,N-dimethyl(meth)acrylamide, useful e.g. to produce textiles - Google Patents

Abstract

Triblock copolymer comprising (a1) a hydrocarbon radical that contains at least two carbon atoms, (b1) a block-B, which contains a statistical copolymer of at least one vinyl aromatic compound (I) and at least one methacrylic acid ester compound (II), (c1) an anchor block-C, which contains a statistical copolymer of at least one compound with (I) and (II), (d1) at least one block-D, which contains a homo or copolymer of N,N-dimethyl(meth)acrylamide, and (a2) at least one further hydrocarbon radical, is claimed. Triblock copolymer comprising (a1) a hydrocarbon radical that contains at least two carbon atoms, (b1) a block-B, which is a statistical copolymer of at least one vinyl aromatic compound of formula (I) and at least one methacrylic acid ester compound of formula (CH 2=C(R3)-C(=O)-OR4) (II), (c1) an anchor block-C, which contains a statistical copolymer of at least one compound comprising (meth)acrylate compounds of formula (IIIa) or (IIIb), or vinyl aromatic compounds of formula (IIIc) with (I) and (II), (d1) at least one block-D, which is a homo or copolymer of N,N-dimethyl(meth)acrylamide, and (a2) at least one further hydrocarbon radical, is claimed. R1 : 1-4C-alkyl; R2 : H (preferred) or 1-4C-alkyl; R3, R5 : H or CH 3; R4 : 4-20C-alkyl; and X : halo. Independent claims are included for: (1) textiles produced or processed with the triblock copolymer, where the textiles are hydrophobically active at 0-50[deg] C, washable in aqueous medium at 55-65[deg] C, and again hydrophobically active after the treatment at 65-85[deg] C; and (2) preparing the triblock copolymers, comprising synthesizing the block-B by adding (III) that is fused with the anchor block-C, and synthesizing the block-D that is bound by the anchor block-C with the block copolymer, where the block-D contains the anchor block-C and block-B. [Image].

Description

wobei die Variablen wie folgt definiert sind:
R¹ gewählt aus C₁-C₄-Alkyl,
R² gewählt aus Wasserstoff und C₁-C₄-Alkyl,
und mindestens einem (Meth)acrylsäureester der allgemeinen Formel II

ist, wobei die Variablen wie folgt definiert sind:
R³ gewählt aus Methyl und Wasserstoff,
R⁴ gewählt aus C₄-C₂₀-Alkyl, verzweigt oder unverzweigt,
(C) einem Ankerblock, der ein statistisches Copolymer von mindestens einer Verbindung, gewählt aus (Meth)acrylaten der allgemeinen Formel IIIa und IIIb,

wobei R⁵ gewählt wird aus Methyl und Wasserstoff,
und Vinylaromaten der Formel IIIc

in denen X gewählt wird aus Halogen,
mit mindestens einem Vinylaromaten der allgemeinen Formel I und mindestens einem (Meth)acrylsäureester der allgemeinen Formel II ist,
(D) mindestens einem Block, der ein Homo- oder Copolymer von mindestens einem N,N-Dimethyl(meth)acrylamid ist,
(A²) mindestens einem weiteren Kohlenwasserstoffrest.The present invention relates to triblock copolymers composed of
(A ¹ ) a hydrocarbon radical which has at least two C atoms,
(B) a block which is a random copolymer of at least one vinyl aromatic of the general formula I.

where the variables are defined as follows:
R ¹ selected from C ₁ -C ₄ -alkyl,
R ^{2 is} selected from hydrogen and C ₁ -C ₄ -alkyl,
and at least one (meth) acrylic ester of the general formula II

is, where the variables are defined as follows:
R ^{3 is} selected from methyl and hydrogen,
R ^{4 is} selected from C ₄ -C ₂₀ -alkyl, branched or unbranched,
(C) an anchor block comprising a random copolymer of at least one compound selected from (meth) acrylates of the general formulas IIIa and IIIb,

wherein R ^{5 is} selected from methyl and hydrogen,
and vinyl aromatics of formula IIIc

where X is selected from halogen,
with at least one vinylaromatic of the general formula I and at least one (meth) acrylic acid ester of the general formula II,
(D) at least one block which is a homo- or copolymer of at least one N, N-dimethyl (meth) acrylamide,
(A ² ) at least one further hydrocarbon radical.

Farther The present invention relates to the use of the invention Triblock copolymers for the manufacture or treatment of textile and a process for the preparation of triblock copolymers according to the invention. Furthermore, the present invention relates to textiles that only heavily soiled and still easy to wash.

To repel dirt, many textiles are provided with a hydrophobic layer. For example, textiles can be impregnated or coated with fluorinated polymers, so-called fluorocarbon resins. In everyday life, however, it can not always be prevented that dirt z. T. also very deep in the textile is registered. The hydrophobic layer on the textile also remains hydrophobic during washing, thereby wetting the fabric with the wash liquor and thereby also the penetration of the wash by means of the textile is difficult. The removal of the dirt during washing is thus hindered by the hydrophobic layer and can lead to deep in the textile registered dirt is very difficult or not completely removed even with very good detergents.

Another method of antisoiling textile equipment is to provide them with a so-called lotus effect ^® , see, for example WO 96/04123 , As a result, textiles are also superhydrophobic, as can be seen at the large critical angles with water. However, if the textile in question should be washed, because a dirt has penetrated very deeply, then the lack of wettability of the textile in question leads to poor washability.

It So the task is to provide textiles, on the one hand are usually heavily polluted, but on the other hand for the case that they are dirty, are very washable.

the Accordingly, the triblock copolymers defined above were used found.

Triblock copolymers of the invention are composed of
(A ¹ ) a hydrocarbon radical, abbreviated remainder (A ¹ ), which has at least two C atoms, for example a C ₂ H ₅ group, preferably a C ₄ H ₉ group, branched or linear, and particularly preferably at least one aromatic group. Very particularly preferably, radical (A ¹ ) has two or three or preferably exactly one aromatic group. The radical (A ¹ ) is preferably different from radicals which are derived from a vinylaromatic of the general formula I. Residual (A ¹ ), in the event that it has at least one aromatic group, a total of 8 to 20 carbon atoms.

wobei
R⁷ gewählt ist aus Phenyl, das ein- bis dreifach mit C₁-C₂-Alkyl substituiert sein kann, beispielsweise para-Methylphenyl, ortho-Methylphenyl, meta-Methylphenyl, 3,5-Dimethylphenyl, para-Ethylphenyl, meta-Ethylphenyl,
oder vorzugsweise unsubstituiert ist,
und
C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl, besonders bevorzugt n-C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, n-Butyl, ganz besonders bevorzugt Methyl.
R⁸ gewählt ist aus C₁-C₄-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, besonders bevorzugt n-C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, n-Butyl, ganz besonders bevorzugt Methyl.In one embodiment of the present invention, radical (A ¹ ) has a functional group, for example an ether or thioether group or preferably an ester group. Most preferably, radical (A ¹ ) is a radical of the formula

in which
R ^{7 is} selected from phenyl which may be mono- to trisubstituted by C ₁ -C ₂ -alkyl, for example para-methylphenyl, ortho-methylphenyl, meta-methylphenyl, 3,5-dimethylphenyl, para-ethylphenyl, meta-ethylphenyl .
or preferably unsubstituted,
and
C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, especially preferably C ₁ -C ₄ -alkyl such as methyl, ethyl, n-propyl, n-butyl, very particularly preferably methyl.
R ^{8 is} selected from C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isobutyl Pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, more preferably nC ₁ -C ₄ - Alkyl such as methyl, ethyl, n-propyl, n-butyl, most preferably methyl.

und mindestens einem (Meth)acrylsäureester der allgemeinen Formel II

ist und im Rahmen der vorliegenden Erfindung auch kurz als Block (B) bezeichnet werden kann, wobei die Variablen wie folgt definiert sind:
R¹ gewählt aus C₁-C₄-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, bevorzugt ist iso-Propyl und besonders bevorzugt tert.-Butyl,
R² gewählt und C₁-C₄-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, und insbesondere Wasserstoff,
R³ ist Methyl oder bevorzugt Wasserstoff,
R⁴ gewählt aus C₄-C₂₀-Alkyl, verzweigt oder vorzugsweise unverzweigt, beispielsweise n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl, n-Dodecyl, iso-Dodecyl, n-Tetradecyl, n-Hexadecyl, n-Octadecyl, n-Eicosyl; bevorzugt unverzweigtes C₄-C₂₀-Alkyl, wie n-Butyl, n-Pentyl, n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Dodecyl, n-Tetradecyl, n-Hexadecyl, n-Octadecyl, n-Eicosyl, insbesondere n-C₆-C₁₂-Alkyl wie n-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Dodecyl.Triblock copolymers according to the invention furthermore exhibit
(B) a block which is a random copolymer of at least one vinyl aromatic of the general formula I.

and at least one (meth) acrylic ester of the general formula II

and in the context of the present invention can also be referred to briefly as block (B), the variables being defined as follows:
R ¹ selected from C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, is preferably isopropyl and especially preferably tert-butyl,
R ^{2 is} selected and C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, and in particular hydrogen,
R ³ is methyl or preferably hydrogen,
R ⁴ selected from C ₄ -C ₂₀ alkyl, branched or preferably unbranched, for example n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo -Pentyl, 1,2-dimethylpropyl, iso -amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, iso-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl; preferably unbranched C ₄ -C ₂₀ -alkyl, such as n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl , n-octadecyl, n-eicosyl, especially nC ₆ -C ₁₂ -alkyl such as n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl.

In Block (B) can be the weight ratio vinylaromatic of the general Formula I to (meth) acrylic acid esters of the general formula II can be chosen arbitrarily. Preferably, the conditions are of vinylaromatic of the general formula I to (meth) acrylic acid ester of the general formula II in a range from 100: 1 to 1: 100, preferably 10: 1 to 1:10 before.

wobei R⁵ gewählt wird aus Methyl und Wasserstoff,
und Vinylaromaten der Formel IIIc

in denen X gewählt wird aus Halogen, beispielsweise Brom und insbesondere Chlor,
mit mindestens einem Vinylaromaten der allgemeinen Formel I und mindestens einem (Meth)acrylsäureester der allgemeinen Formel II ist, die wie vorstehend definiert sind.Triblock copolymers according to the invention have
(C) an anchor block, also referred to for short as anchor block (C), which is a random copolymer of at least one compound selected from (meth) acrylates of general formula IIIa and IIIb,

wherein R ^{5 is} selected from methyl and hydrogen,
and vinyl aromatics of formula IIIc

in which X is selected from halogen, for example bromine and in particular chlorine,
with at least one vinylaromatic of the general formula I and at least one (meth) acrylic acid ester of the general formula II, which are as defined above.

preferred Examples of compounds of formula III c are each para-substituted derivatives and in particular para-chloromethylstyrene (Para-Chlorbenzylstyrol).

Prefers anchor block (C) is a random copolymer of compound of Formula III a.

In Anchor block (C) can be the weight ratio of vinyl aromatic of general formula I to (meth) acrylic acid esters of the general Formula II to (meth) acrylate of general formula III chosen arbitrarily become.

In an embodiment of the present invention is the Weight ratio of vinyl aromatic of the general formula I to (meth) acrylic acid esters of the general formula II in Block (B) and anchor block (C) are the same.

In another embodiment of the present invention the weight ratio of vinyl aromatic is the general one Formula I to (meth) acrylic acid esters of the general formula II in block (B) and anchor block (C) different.

invention Triblock copolymers continue to exhibit

• (D) at least one block which is a homo- or copolymer is at least one N, N-dimethyl (meth) acrylamide and in the context of the present invention may also be referred to briefly as block (D).

there it is preferably a homo- or copolymer of N, N-dimethylacrylamide. As a comonomer, for example, (meth) acrylic acid is suitable.

Triblock copolymers according to the invention furthermore exhibit
(A ² ) at least one further hydrocarbon radical, which may be the same or preferably different from the radical (A ¹ ) and in the context of the present invention also briefly rest (A ² ) is called.

The radical (A ² ) can have 1 to 20 C atoms.

In one embodiment of the present invention, radical (A ² ) has 1 to 20 C atoms and one or more heteroatoms, for example oxygen or, in particular, sulfur.

wobei R⁶ gewählt wird aus
R⁶ gewählt aus C₆-C₁₀-Aryl, ein oder mehrfach substituiert, beispielsweise mit C₁-C₄-Alkyl, insbesondere mit Methyl, oder vorzugsweise unsubstituiert, und
S-C₁-C₄-Alkyl, bevorzugt S-n-C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl oder n-Butyl, besonders bevorzugt Methyl.In a particularly preferred embodiment of the present invention, radical (A ² ) has the following formula V:

wherein R ^{6 is} selected from
R ^{6 is} selected from C ₆ -C ₁₀ -aryl, mono- or polysubstituted, for example with C ₁ -C ₄ -alkyl, in particular with methyl, or preferably unsubstituted, and
SC ₁ -C ₄ alkyl, preferably SnC ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl or n-butyl, particularly preferably methyl.

In an embodiment of the present invention Block (B) has a degree of polymerization in the range of 10 to 500, preferably up to 300, more preferably up to 200 on.

In an embodiment of the present invention Anchor block (C) a degree of polymerization (number average) in the range from 1 to 100, preferably from 2 to 20.

In an embodiment of the present invention Block (D) has a degree of polymerization (number average) in the range of 10 to 500, preferably up to 300, more preferably up to 200 on.

In an embodiment of the present invention Anchor block (C) each have a lower degree of polymerization than the blocks (B) and (D) on. Preferably, the degree of polymerization is in anchor block (C) a maximum of 30% of the degree of polymerization of block (B) and block (D).

In an embodiment of the present invention degrees of polymerization of block (B) and block (D) in the range from 1: 2 to 2: 1, preferably 1.5: 1 to 1: 1.5.

In one embodiment of the present invention, vinylaromatic of the general formula I is characterized in that R ^{1 is} para to the vinyl group and that R ^{2 is} hydrogen.

The Allow degrees of polymerization of block (B), block (C) and block (D) for example, determined by GPC (gel permeation chromatography). This can be done, for example, so that one at the end a synthesis step (see below) takes a sample and the molecular weight or the degree of polymerization determined. The degree of polymerization of Block (B) can be determined directly, that of block (C) or block (D) is determined and subtracted the corresponding molecular weights from block (B) or block (B) and block (C).

In one embodiment of the present invention, the molecular weight distribution of triblock copolymer according to the invention is narrow. For example, the quotient M _w / M _n may range from 1.01 to a maximum of 3, preferably up to a maximum of 2 lie.

In an embodiment of the present invention Block (D) is a homopolymer of N, N-dimethylacrylamide.

In an embodiment of the present invention triblock copolymer according to the invention a hydrophilic and a hydrophobic block, wherein block (B) is hydrophobic and Block (D) hydrophilic.

there should be understood to mean hydrophobic that the intrinsic contact angle of the relevant random copolymer based on block (B) is at least 90 ° with water at room temperature. Accordingly, hydrophilic is understood to mean that the intrinsic contact angles of the homo- or copolymer in question, the block (D) is based, with water at room temperature less than 90 °; preferably less than 85 °. The respective ones intrinsic contact angles are used, for example, on films of the relevant random copolymer based on block (B), or on films of the relevant homo- or copolymer, the block (D), determined.

In an embodiment of the present invention Triblock copolymers according to the invention or block (B) of triblock copolymers according to the invention a glass transition temperature in the range of 55 to 65 ° C ascertainable, for example, by DSC (differential thermal analysis), second heating cycle.

In an embodiment of the present invention Triblock copolymers of the invention further glass transition at temperatures above 70 ° C have.

In one embodiment of the present invention, triblock copolymers according to the invention may be represented by a molecular formula as follows:

there are the units in square brackets for statistical copolymers of the comonomers in question. anchor block (C) starts at the point where the first comonomer.

One Another object of the present invention are textiles that at temperatures in the range of 0 ° C to 50 ° C hydrophobic act, at temperatures in the range of preferably 55 ° C. to 65 ° C in aqueous medium, for example in aqueous liquor, are washable and after a treatment at a temperature above 65 ° C to 85 ° C again appear hydrophobic. Treatment with treatment above 65 ° C to 85 ° C is preferably in the air or carried out under inert gas. inventive Textile does not easily soil, but is at temperatures in the range from 55 ° C to 65 ° C hydrophilic and leaves wash well. At temperatures above 65 ° C to 85 ° C switches textile according to the invention again on hydrophobic.

inventive Textile is resistant to abrasion, that is, those described above Properties remain even after several washing and drying cycles receive.

For the purposes of the present invention, textile or textile substrates are to be understood as meaning textile fibers, semi-finished and finished textile products and finished articles made thereof, which, in addition to textiles for the clothing industry, also include, for example, carpets and other home textiles as well as textile structures serving technical purposes. These include unshaped structures such as flakes, linear structures such as twine, threads, filaments, yarns, linen, cords, ropes, threads and body structures such as felts, fabrics, knitted fabrics, nonwovens and wadding. Textile may be of natural origin, for example cotton, wool or flax, or synthetic, for example polyamide, polyester, modified polyester, polyester blend, polyamide blend, polyacrylonitrile, triacetate, acetate, polycarbonate, poly propylene, polyvinyl chloride and polyester microfibers. Especially preferred are cotton and blends of cotton with synthetic fibers.

One Another object of the present invention is the use of triblock copolymers of the invention to Production or treatment of textile. Another item The present invention is a process for the preparation or Treatment of textile using inventive Tri-block copolymers. Another object of the present invention are textiles made using or treated with at least one triblock copolymer according to the invention.

The Treatment of textile according to the invention can be for example, by the manner of a coating method, for example with the aid of a coating paste or with a foam coating, or in the manner of an extraction process. Particularly preferred is the use of a foulard.

Textile For the purposes of the present invention can be pretreated or pretreated bleached, for example, especially in the case of cotton, furthermore dyed, pigmented, printed or functionally equipped, for example easy to iron, easy to iron, non-iron, flameproof, antimicrobial and / or odor-inhibiting.

Textile For the purposes of the present invention can be equipped hydrophobic be. In a preferred variant of the present invention is However, it is not hydrophobic equipped textile Textile.

Textile For the purposes of the present invention can be made or preferably not made up. If you are not ready made Textile with inventive triblock copolymer treated, one speaks in the context of the present invention also of inventive textile production process.

In an embodiment of the present invention brings Inventive Triblockcopolymer in aqueous Fleece on non-ready-made textile on.

In an embodiment of the present invention the aqueous liquor used for application to textile one or more auxiliary agents, for example wetting agents, defoamers (Foam inhibitors), aeration agents, crosslinkers (hardeners), Flow control agents and thickeners, and in particular polyvinyl acetate, Polyvinyl alcohol or partially saponified polyvinyl acetate.

When Auxiliary can be one or more wetting agents use, by way of example are alkylpolyglycosides, alkylphosphonates, alkylphenylphosphonates, To name alkyl phosphates and alkylphenyl phosphates.

When Auxiliary can be one or more defoamers (foam inhibitors) use, for example, are liquid at room temperature Silicones, not ethoxylated or ethoxylated one or more times, to call.

mit Molekulargewichten M_w im Bereich von 100.000 bis 2.000.000 g/mol zu nennen, in denen R⁹ für Methyl oder vorzugsweise Wasserstoff steht. Als Beispiele für Verdickungsmittel natürlichen Ursprungs seien genannt: Agar-Agar, Carrageen, modifizierte Stärke und modifizierte Cellulose.As an aid, one or more thickening agents can be added, which may be of natural or synthetic origin, for example. Suitable synthetic thickeners are poly (meth) acrylic compounds, polycarboxylic acids, polyethers, polyimines, polyamides such as polyacrylamide, and polyurethanes. In particular, copolymers with 85 to 95% by weight of acrylic acid, 4 to 15% by weight of acrylamide and about 0.01 to 1% by weight of the (meth) acrylamide derivative of formula VI

with molecular weights M _w in the range of 100,000 to 2,000,000 g / mol, where R ^{9 is} methyl or preferably hydrogen. Examples of thickening agents of natural origin include: agar-agar, carrageenan, modified starch and modified cellulose.

As an aid you can use one or more crosslinkers (hardeners). Examples are isocyanurates and in particular hydrophilized isocyanurates and also mixed hydrophilicized diisocyanates / isocyanurates, for example isocyanurate of hexamethylene diisocyanate (HDI) reacted with C ₁ -C ₄ -alkylpolyethylene glycol. Examples of such crosslinkers are for example EP-A 0 486 881 known. Further examples are oxime capped isocyanates / diisocyanates / isocyanurates, in particular butoxime-capped diisocyanate te and butoxime-sealed isocyanurates.

When Aids can be one or more flow aids, for example, ethylene glycol.

When Aids can be one or more aerating agents use, for example, one or more Guerbet alcohols, easy or up to ten times ethoxylated.

When The preferred adjuvant can be polyvinyl acetate, polyvinyl alcohol or partially saponified polyvinyl acetate, in particular to 0.1 to 75 mol% partially saponified polyvinyl acetate. Further preferred Auxiliaries are mixtures of polyvinyl acetate or partially saponified Polyvinyl acetate and polyvinyl alcohol.

As an aid you can use weak acids or weak bases as pH regulators. Suitable examples are ammonium salts such as NH ₄ Cl and (NH ₄ ) ₂ SO ₄ . Furthermore, carboxylic acids are suitable such as acetic acid or citric acid.

As an aid you can use one or more biocides. Examples of biocides are for example 1,2-benzisothiazolin-3-one ( "BIT") (commercially available as Proxel ^® brands from. Avecia Lim.) And call its alkali metal salts, other suitable biocides are 2-methyl-2H- isothiazol-3-one ("MIT") and 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT"). In general, 10 to 150 ppm of biocide are sufficient, based on aqueous liquor.

wishes according to the invention by triblock copolymer Foam coating to apply on textile, so you can in addition use one or more foam surfactants.

In an embodiment of the present invention the aqueous liquor used for treating textile a solids content in the range of 1 to 60%, preferably 30 up to 40%.

In an embodiment of the present invention the aqueous liquor used for treating textile in the range of 10 to 120 g / l according to the invention Triblock copolymer, preferably 20 to 80 g / l.

The Fleet temperature in the implementation of the invention Textile manufacturing process is not critical per se. The temperature may be in the range of 10 to 95 ° C, preferably 20 to 40 ° C.

The Treating textile in the context of the invention Textile manufacturing process can be made according to common methods perform the textile treatment, for example by one or more spraying, sprinkling, squeezing, pouring over or printing. In particular, one can treat textile with Help with a foulard. Preference is also the Application by knife coating in the sense of a coating process.

The Fleet recording can be chosen so that a fleet recording from 5% to 85% by weight, preferably from 10 to 70% by weight.

The The textile production process according to the invention can one can perform in common machines for the equipment of textiles are used, in particular Foulards. Particularly suitable are foulards with vertical textile feed, which contain as an essential element two rollers pressed against each other the textile is led. Above the rollers is the Liquid filled and wets the textile. By pressing the textile is squeezed and a constant Order guaranteed. Preferred are foulards, the one Have the tub in which the textile with aqueous formulation soaks and connected to a pair of horizontal rollers is, through which the textile is led. By the pressure the textile is squeezed off and a constant order is guaranteed.

In another preferred embodiment of the present invention Invention brings a preferably aqueous formulation, contains the triblock copolymer according to the invention, with a squeegee on, for example, a knife blade, an air knife or a roller blade.

in the Connection to the actual inventive Textile manufacturing process can be that with inventive Triblock copolymer treated textile according to customary in textile industry Dry methods.

To the Drying can be done, for example, at atmospheric pressure. But you can work at reduced pressure instead, for example, at a pressure in the range of 1 to 850 mbar.

To the Drying can be carried out with an optionally heated gas stream work, in particular with an optionally heated inert gas stream such as nitrogen. If you want a heated gas stream For example, temperatures are in the range of 30 to 200 ° C, preferably 120 to 180 ° C, especially preferably 140 to 170 ° C suitable.

in the Connection to the actual inventive Textile manufacturing process and optionally drying can thermally treated, continuously or discontinuously. The duration of the thermal treatment can be within wide limits choose. Usually one can over the Duration of about 10 seconds to about 30 minutes, especially 30 Thermally treat for up to 5 minutes. To carry out A thermal treatment is heated to temperatures of up to at 180 ° C, preferably up to 150 ° C. Naturally it is necessary to indicate the temperature of the thermal treatment to adjust the sensitivity of the textile.

suitable Method for thermal treatment, for example, a hot air drying, especially drying in the tenter frame, continue ironing, Calendering, shrinking, sanforizing and monforating.

To the implementation of the invention Textile production process is obtained according to the invention Textile that can be made up.

inventive Textile may, for example, in the range of 0.5 to 5 wt .-% inventive triblock copolymer have, based on the weight of the goods, if you put it through a exhaust process has applied.

Textile according to the invention can have a circulation in the range from 0.5 g / m ² to 5 g / m ² triblock copolymer according to the invention, if it has been applied by a coating process.

In An embodiment of the present invention can be before the actual treatment of textile with inventive Triblockcopolymer apply a primer. Examples especially for cotton suitable adhesion promoter are polyglycidyl methacrylate and polyglycidyl acrylate. To an improved Adhesion of triblock copolymer according to the invention on synthetic fibers are amino, hydroxyl or carboxyl groups containing per se known binder polymers suitable as primer.

In another embodiment of the present invention one can already pre-fabricated textile with inventive Treat triblock copolymer, for example by spraying with an aqueous formulation of inventive Triblock.

inventive Textile has good hydrophobicity at room temperature. at Temperatures around 60 ° C change the orientation the polymer side chains of inventive Triblock copolymer on textile, and the textile surface acts hydrophilic. Under conditions of delicates in the Washing machine can thus the wash liquor according to the invention Moisten textile and eliminate deeply penetrated dirt. At the subsequent drying, for example on the clothesline or in the tumble dryer or at the latest after the Ironing oriented the Polymersei tenketten of the invention Triblockcopolymers again, and the relevant inventive Textile again has a hydrophobic effect.

Of the Switching effects hydrophobic-hydrophilic are multiply reversible, according to the invention Textile loses these properties even after at least 10 household washes (60 ° C) not. In one embodiment of the present invention Invention is inventive Textile in order with triblock copolymer according to the invention treated cotton or cotton blended fabric, which is a washing resistance of 40 multiple washes at 60 ° C.

One Another aspect of the present invention is a method for Preparation of Triblock Copolymers According to the Invention in the following also as inventive production process designated.

The The preparation process according to the invention can be so perform that one first a block (B) synthesized by adding comonomer of the general formula III attaches an anchor block (C) and then a block (D) synthesized via the anchor block (C) with the block copolymer having the anchor block (C) and block (B).

there the variables (B), (C) and (D) are as defined above.

The preparation process according to the invention can be carried out by a stepwise copolymerization, which is carried out in the presence of compounds having radicals (A ¹ ) and (A ² ).

In a preferred embodiment of the present invention, the preparation process according to the invention is carried out by carrying out the synthesis in the presence of a chain transfer agent which has hydrocarbon radicals which correspond to the radicals (A ¹ ) and (A ² ).

R⁶ gewählt aus C₆-C₂₀-Aryl, substituiert oder unsubstituiert, und S-C₁-C₄-Alkyl,
R⁷ gewählt aus C₁-C₁₀-Alkyl und Phenyl, unsubstituiert oder ein bis dreifach substituiert mit C₁-C₂-Alkyl,
R⁸ gewählt aus C₁-C₄-Alkyl.In a preferred embodiment of the present invention, the preparation process according to the invention is carried out by using as chain transfer agent a substance of the general formula IV in which the variables are defined as follows:

R ^{6 is} selected from C ₆ -C ₂₀ -aryl, substituted or unsubstituted, and SC ₁ -C ₄ -alkyl,
R ^{7 is} selected from C ₁ -C ₁₀ -alkyl and phenyl, unsubstituted or monosubstituted to trisubstituted by C ₁ -C ₂ -alkyl,
R ⁸ selected from C ₁ -C ₄ alkyl.

In this case, R ⁶ , R ⁷ and R ^{8 are} substituted as above.

Many substances of the general formula IV are known per se and can be purified by or in analogy with S. Perrier et al., Macromolecules 2004, 37, 2709-2717 synthesize.

In an embodiment of the present invention leads one the manufacturing process according to the invention so by passing blocks (B), (C) and (D) through each produces radical copolymerization.

When Radical starters can be used as radical initiators (Initiators), for example peroxides or preferably Azo compounds. Example of a particularly suitable Azo compounds is azobisisobutyronitrile (AIBN). The initiation can be done photochemically or preferably thermally.

In an embodiment of the present invention sets for the synthesis of triblock copolymer according to the invention Chain transfer in excess to the radical starter a, for example in a weight ratio in the range from 10: 1 to 5: 1.

The individual synthesis steps can be in bulk or preferably in organic solvent. suitable Solvents are, for example, tetrahydrofuran (THF), 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, toluene, the isomers Xylenes and especially anisole.

In an embodiment of the present invention leads at the manufacturing process according to the invention Temperatures in the range of 50 to 100 ° C, preferably 55 up to 90 ° C.

In an embodiment of the present invention leads one the manufacturing process according to the invention at normal pressure through. In another embodiment The present invention leads to the invention Production method at elevated pressure by, for example at 2 to 15 bar.

In an embodiment of the present invention leads one on the production process according to the invention a period of 2 to 200 hours.

In a preferred embodiment of the present invention leads to the production process of the invention after a RAFT polymerization by (English, Reversible Addition Fragmentation chain transfer polymerization).

In an embodiment of the present invention leads one the manufacturing method of the invention under Protective gas, for example under a noble gas atmosphere, especially under argon, or under a nitrogen atmosphere.

In one embodiment of the present invention can be obtained after obtaining block copolymer the blocks (B) and (C), which is saturated by the radicals (A1) and (A2), purify, for example by precipitation or reprecipitation with ethanol or methanol. In another embodiment of the present invention, block copolymer of blocks (B) and (C), which is saturated by the radicals (A1) and (A2), can be further processed in situ.

By the production process according to the invention can be Triblock copolymer according to the invention in good yields and excellent purity.

One Another object of the present invention is the use of textiles according to the invention as or for the production of sportswear, including hiking clothing, such as jackets, Shirts, pants, T-shirts and camisole. Another object of the present invention is the use of the invention Textiles as or for the production of protective clothing, for example Rain jackets, rain pants or workwear, preferably of such Workwear where as complete as possible Cleaning is required, for example in the medical service or in food production or food processing.

The Invention will be explained by working examples.

I. Representation of inventive Triblock copolymer (T-Copo.1)

I.1 Preparation of Block Copolymer (A1) - (B.1) - (C.1) - (A2)

The reagent of formula (IV.1) was after S. Perrier et al., Macromolecules 2004, 37, 2709-2717 synthesized.

The Solvent anisole (Acros, 99%) and the comonomers 4-tert-butylstyrene (I.1) (Aldrich, 93%) and n-hexyl acrylate (II.1) (Aldrich, 98%) distilled in vacuo over calcium hydride (Fluka, ≥ 97%). AIBN (Fluka, ≥ 98%) was purified from diethyl ether for purification recrystallized once. N-acryloxysuccinimide (III.1) (Acros, 99%) was used as supplied without further purification steps.

The Copolymerizations were each under a protective gas atmosphere carried out by mixing the reaction mixtures with liquid Nitrogen froze, evacuated, saturated with argon and thawed again. These operations were repeated three times. After that the reaction mixture was free of measurable amounts of oxygen.

Preparation of Block Copolymer (A1.1) - (B.1) - (C.1) - (A2.1) by RAFT Polymerization Into a 20 ml snap-cap glass were successively added the reagent of formula (IV.1) (38 , 05 mg, 0.126 mmol), 4-tert-butylstyrene (1.1) (4.019 g, 25.08 mmol), n-hexyl acrylate (11.1) (1.9691 g, 12.60 mmol) and 0.5 g ( 2.08 mg, 0.0127 mmol) of an AIBN anisole solution (20 mg AIBN dissolved in 5 g anisole) and 4.5 g anisole added via syringe. The solution was then transferred to a 100 ml Schlenk flask and deoxygenated. The copolymerization was started by immersing the Schlenk flask in a temperature controlled at 60 ° C bath. After a polymerization time of 64 hours and 30 minutes, a solution consisting of 1 g (5.9 mmol) of N-acryloxysuccinimide (III.1) (Acres Chemicals, 99%) and 3 g of anisole in countercurrent to the argon was added to the reaction mixture. Prior to the addition of this monomer solution, the above operations are performed 4 times to remove any infiltrated oxygen. The mixture was then further copolymerized for 3 hours and 30 minutes before the reaction was stopped by cooling the reaction flask (liquid nitrogen) and admission of air. To purify the block copolymer (A1.1) - (B.1) - (C.1) - (A2.1), the reaction mixture was added dropwise to ethanol cooled to -78 ° C and the block copolymer
(A1.1) - (B.1) - (C.1) - (A2.1) failed. Block copolymer (A1.1) - (B.1) - (C.1) - (A2.1) was filtered off with suction and dissolved in 12 ml of ethyl acetate. Thereafter, block copolymer (A1.1) - (B.1) - (C.1) - (A2.1) was again cold Ethanol (-78 ° C) precipitated and then filtered with suction. Dissolution in 12 ml of ethyl acetate and precipitation with ethanol was repeated once more. Thereafter, no residual comonomer could be detected. Block copolymer (A1.1) - (B.1) - (C.1) - (A2.1) was pre-dried in vacuo at room temperature and then freeze-dried with benzene (Fluka, ≥ 99.5%).

Mol ratios of the reactants at the beginning of the RAFT polymerization: 4-tert-butylstyrene: n-hexyl acrylate: (IV.1): AIBN 200 100 1 0.1

The structure and composition of the block copolymer (A1.1) - (B.1) - (C.1) - (A2.1) were examined by NMR spectroscopy.
¹ H-NMR (CDCl _3): δ [ppm] = 7.4-6.9 (H-5), 6.9 to 6.2 (H-4), 4.0 to 3.2 (H 12), 3.1-2.5 (H-22), 2.5-1.0 (H-1, H-2, H-8 through H-10, H-13 through H-16, H 18, H-19), 0.91 (H-17).
¹³ C-NMR (CDCl _3): δ [ppm] = 175.6 (C-11), 171.2 (C-20), 169.1 (C-21), 148.4 (C-6), 144-139 (C-3), 127.4 (C-4), 124.7 (C-5), 63.8 (C-12), 46-38 (C-1, C-2, C-) 9, C-10, C-18, C-19), 34.2 (C-7), 31.4 (C-8, C-15), 28.4 (C-13), 25.6 ( C-14, C-22), 22.5 (C-16), 14.0 (C-17).
FTIR:
IR bands [cm ^-1 ] = 3088, 3053, 3024, 2960, 2932, 2867, 1901, 1811, 1783, 1734, 1511, 1462, 1412, 1393, 1362, 1269, 1203, 1161, 1111, 1065, 1017 , 829, 645, 581

The molecular weight M _n and the polydispersity of the block copolymer (A1.1) - (B.1) - (C.1) - (A2.1) were determined by GPC with chloroform as solvent. In order to establish a calibration function between molecular weight M _n and the elution volume, narrowly distributed polystyrene standards were used.

M _n of block copolymer (A1.1) - (B.1) - (C.1) - (A2.1): 22,100 g / mol. Polydispersity 1.13. Taking into account the respective monomer conversions, a molecular weight M _n for the hydrophobic block (B.1) and the anchor block (C.1) and thus also for block copolymer (A1.1) - (B.1) can be determined with the aid of NMR spectroscopy. - (C.1) - (A2.1). The respective calculated molecular weights M _{n, cal} were in detail: M n, Cal (Anchor block) = 4,500 g / mol

I.2 Preparation of Inventive Triblock copolymer (T-Copo.1) from block copolymer (A1) - (B.1) - (C.1) - (A2)

For Synthesis of Triblock Copolymer of the Invention Poly [(4-tert-butylstyrene-r-hexylacrylate) -block (4-tert-butylstyrene-r-hexylacrylate-r-N-acryloxysuccinimide) -block- (N, N-dimethylacrylamide)] was block copolymer (A1.1) - (B.1) - (C.1) - (A2.1) as a macro-transfer reagent or Macro CTA used.

Into a 20 ml snap-cap jar were gradually added 0.4415 g (0.0147 mmol) of macro CTA, 2.5 g of anisole, 1.0146 g (10.2 mmol) of N, N-dimethylacrylamide (≥ 98%, Fluka ) and 60 μl (0.00147 mmol) of an AIBN-anisole solution (20.3 mg AIBN dissolved in 5.0365 g anisole.) After mixing all the components, the reaction mixture was transferred to a Schlenk tube and the oxygen was removed After a polymerization time of 40 hours and 40 minutes, the polymerization was stopped by cooling the reaction mixture (indirectly with liquid nitrogen) and subsequent admission of air, after which all volatile components were removed in an oil pump vacuum. For further purification, the triblock copolymer according to the invention was freeze-dried with benzene (100 ml): molar ratios of the reactants at the beginning of the RAFT polymerization: N, N-dimethyl: Macro-CTA: AIBN 700 1 0.1

Analytical data:

The structure and composition of the triblock copolymer were examined and verified by ¹ H and ¹³ C NMR spectroscopy.
¹ H-NMR (CDCl _3): δ [ppm] = 7.4-6.9 (H-5), 6.9 to 6.2 (H-4), 4.0 to 3.2 (H 12), 3.2-2.8 (H-22, H-26), 2.8-2.3 (H-24), 2.3-1.0 (H-1, H-2, H-8 to H-10, H-13 to H-16, H-18, H-19, H-23), 0.91 (H -17).
¹³ C-NMR (CDCl _3): δ [ppm] = 175.6 (C-11), 174.6 (C-25), 171.1 (C-20), 169.1 (C-21), 148.3 (C-6), 144-139 (C-3), 127.4 (C-4), 124.7 (C-5), 63.8 (C-12), 46-38 (C -1, C-2, C-9, C-10, C-18, C-19), 38-33.5 (C-23, C-24, C-26), 34.2 (C-7 ), 31.4 (C-8, C-15), 28.4 (C-13), 25.5 (C-14, C-22), 22.5 (C-16), 14.0 ( C-17).
FT-IR:
IR bands [cm ^-1 ] = 3088, 3052, 3022, 2956, 2930, 2861, 1902, 1810, 1782, 1735, 1643, 1497, 1461, 1398, 1360, 1260, 1204, 1140, 1096, 1061, 829 , 752, 664, 625, 581

The molecular weight M _n and the polydispersity of the triblock copolymer according to the invention (T-Copo.1) were determined by means of GPC with dimethylacetamide as solvent, which contained 2% by volume of water and 3 g / l of LiCl. For establishing a calibration function between molecular weight and elution volume, narrowly distributed poly (2-vinylpyridine) standards were used.

M _n for triblock copolymer according to the invention (T-Copo.1) was 60,000 g / mol.

The Polydispersity was 1.9. This increase was on the broad molecular weight distribution of the hydrophilic poly (N, N-dimethylacrylamide) block and showed up in the GPC elution curve through a shoulder.

The calculated molecular weight M _n for the block (D.1) was 37,000 g / mol.

Further investigations:

The Determination of glass transition temperature was using the DSC performed. It was 59 ° C. One determined another glass transition at 125 ° C.

II. Inventive Treatment of textile

A textile treatment according to the invention is carried out using the example of cotton. This was based on cotton fabric with a basis weight of 196 g / m ² .

Preparation of Adhesion Promoter Layer: In a filtered (Teflon filter: pore size: 0.2 μm) solution of poly (glycidyl methacrylate) (0.1 wt% in CHCl ₃ ) was white cotton fabric (7 x 1.4 cm ² ) for 30 seconds immersed, then pulled out and dried in air. Thereafter, the fabric is annealed for 20 min at 100 ° C in vacuo. Unattached PGMA was removed by repeated extraction with chloroform.

After that was a 2 wt .-% solution of inventive Triblock copolymer (T-Copo.1) dried over calcium hydride Tetrahydrofuran (THF) prepared as a solvent and then filtered (Telfonfilter: pore diameter 0.2 μm). In this solution of (T-Copo.1) was dipped the cotton fabric provided with the primer layer. After 30 seconds, it was pulled out again, dried in air and then for 16 hours at 150 ° C in a vacuum annealed. After annealing was untethered invention Triblock copolymer by extraction with THF as solvent (nine times in total) at room temperature.

you received textile according to the invention (BW.1).

Has been a water droplet on a according to hydrophil switched inventive Textile (BW.1) applied (switching in 60 ° C hot Water), this waterdrop was in significantly less than 1 Second shot of (BW.1). The water droplet wetted according to the invention Textile (BW.1) complete. The measurement of a contact angle was therefore not possible.

The Downstream from hydrophilic to hydrophobic can already at a temperature of about 75 ° C in the tumble dryer or with a correspondingly hot hair dryer become. If a water droplet is switched to hydrophobic according to the invention Textile (BW.1) applied, so this drop of water had a static Contact angle of about 130 °.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 96/04123 [0004]
• - EP 0486881 A [0050]

Cited non-patent literature

• - Perrier et al., Macromolecules 2004, 37, 2709-2717 [0083]
• - S. Perrier et al., Macromolecules 2004, 37, 2709-2717 [0097]

Claims (15)

Triblock copolymers, composed of (A ¹ ) a hydrocarbon radical having at least two carbon atoms, (B) a block which is a random copolymer of at least one vinyl aromatic of the general formula I.

where the variables are defined as follows: R ¹ selected from C ₁ -C ₄ -alkyl, R ² selected from hydrogen and C ₁ -C ₄ -alkyl, and at least one (meth) acrylic ester of the general formula II

wherein the variables are defined as follows: R ^{3 is} selected from methyl and hydrogen, R ^{4 is} selected from C ₄ -C ₂₀ alkyl, branched or unbranched, (C) an anchor block which is a random copolymer of at least one compound from (meth) acrylates of the general formula IIIa and IIIb,

wherein R ^{5 is} selected from methyl and hydrogen, and vinyl aromatic compounds of formula IIIc

in which X is selected from halogen, with at least one vinyl aromatic of the general formula I and at least one (meth) acrylic acid ester of the general formula II, (D) at least one block which is a homo- or copolymer of N, N-dimethyl (meth ) acrylamide, (A ² ) at least one further hydrocarbon radical. Triblock copolymers according to claim 1, characterized in that that block (B) has a degree of polymerization (number average) in the range from 10 to 500. Triblock copolymers according to claim 1 or 2, characterized in that block (D) has a degree of polymerization (number average) ranging from 10 to 500. Triblock copolymers according to any one of claims 1 to 3, characterized in that R ^{1 is} in para-position to the vinyl group and that R ^{2 is} hydrogen. Triblock copolymer according to one of the claims 1 to 4, characterized in that block (C) has a degree of polymerization (Number average) in the range of 1 to 100. Triblock copolymers according to any one of claims 1 to 5, characterized in that at block (D) is a Homopolymer of N, N-dimethylacrylamide is. Use of triblock copolymers according to one of Claims 1 to 6 for the production or treatment of textile. Process for the preparation or treatment of textile using at least one triblock copolymer according to one of claims 1 to 6. Textiles that are at temperatures in the range of 0 ° C to 50 ° C hydrophobic, at temperatures in the range from 55 ° C to 65 ° C in aqueous medium are washable and after a treatment at a temperature above from 65 ° C to 85 ° C again hydrophobic act. Textiles made using or treated with at least one triblock copolymer according to one of Claims 1 to 6. Textiles according to claim 9, characterized that they are manufactured using or treated with at least one triblock copolymer according to any one of claims 1 to 6. Process for the preparation of triblock copolymers according to one of claims 1 to 6, characterized that one first synthesized a block (B), by Addition of comonomer of general formula III an anchor block (C) attaches and then synthesizes a block (D) over the anchor block (C) is connected to the block copolymer, the anchor block (C) and block (B). A method according to claim 12, characterized in that one carries out the synthesis in the presence of a chain transfer agent having hydrocarbon radicals corresponding to the radicals (A ¹ ) and (A ² ). Process according to Claim 13, characterized in that the chain transfer agent used is a substance of the general formula IV in which the variables are defined as follows:

R ^{6 is} selected from C ₆ -C ₁₀ -aryl, substituted or unsubstituted, and SC ₁ -C ₄ -alkyl, R ^{7 is} selected from C ₁ -C ₁₀ -alkyl and phenyl, unsubstituted or one to three times with C ₁ -C ₂ alkyl, R ⁸ selected from C ₁ -C ₄ alkyl. Use of textiles according to claim 10 or 11 as or for the production of sports or protective clothing.